Water-resistant, starch-containing, product and method



35 starch which is in a dehydrated condition, that has been adsorbed approximately 10% by Weight 5 Patented Jul 11, 1939 1 2,165,834

WATER-RESISTANT, STARCH-CONTAINING, PRODUCT AND METHOD Harold E. Bode, Ghicago, Ill., asslgnor, by mesne assignments, to Corn Products Refining Company, New York, N. Y., a corporation of New Jersey No Drawing. Application September 20, 1937,

Serial No. 164,796

6 Claims. (Cl. 13416) This invention relates to the production of An illustrative example of the production of Water-immiscible -or water-resistant substances, the dehydrated starch, according to the aforesuch as water resistant coatings, paint, lacquer, mentioned copending application is as follows: varnish, greases and the like, and the principal 11.2 grams of starch were vacuum dried to con- 5 object of the invention is to provide substances stant weight. To the resulting 10.2 grams of dry 5 of 'the nature described in which one of the inanhydrous starch was added 13 grams of progredients is starch. 'pylene di-chloride which was thereupon rapidly Another object is to provide a starch paste adsorbed into the dry starch, care being exercised which is devoid of water, and, for thatreason, is during the addition of the propylene di-chloride particularly adapted for use as a filler, gel or to avoid the access of air. The resulting powder 10 thickening agent for water-immiscible subof starch-propylene di-chloride,'when spread on stances. a shallow tray and allowed to stand at room tem Further objects will more fully appear from perature with thorou h air exposure, showed 110 the following detailed description. increase of weight, 1. e. no adsorption of moisture 5 Starch has heretofore been extensively utilized om th for thirty hours As seen as the 15 as a filler, gel or thickening agent, in waterpropylene di-chloride had volatilized the starch miscible substances and the high qualities of egan to ake up m i r fr the air. starch or starch paste for such purposes are well According to the present invention the de-, recognized. .However, until the present time no hydrated sta h, pr u d as above fly d satisfactory method has been devised for utilizing scrib d, is fi st eat o form an anhydrous 20 these qualities of starch in the field of waterstarch paste, in which form it is adap for I111!!- immiscible substances, such as above described. mg w t va io W cible subs e The primary reason for the non-use of starch this p o it has been found that Various in this field is that starch, even in an air dry free, Organic qu d s ch '85 y w 8171-, and

state, contains from 5% to 15% or more moisture, heterocycllc ami es, c lo al d the like are 25 depending upon the type of starch and the atstarch swelling agents, t at i y P ss. the mospheric conditions. Consequently if ordinary power of making the starch gel and form a paste. air dried starch were mixed with a water im- T e foll w ng two xa pl s i us t t us miscible substance, such as paint, for example, of chloral and a heterocye ie am p the moisture content in the starch would resist tively, in e pre-tl'eetmentref the starch to form 30 mixing with the ingredientsof the paint and dea water-free starch paste. stroy the value of the product. Example 1 The present invention contemplates the introduction nt water ,immiscib1e substances of Into 10 parts of dehydrated starch (into which is, starch which has substantially zero water of P py e e e e) thoroughly mix 100 pa s content and has b t t t render t relaof chloral at room temperature. The chloral will tively stable in t presence'of am react with the starch to gelatinize the same to I The production of dehydrated and relatively form a water-free, chloral-starch paste. If de- 40 stable starch, such as is utilized in carrying out sired. the mixture can e heated to F. to 40 the present invention, is fully described in my distill fi the p py dlehlerldecopending application Serial No. 159,382, filed Example 2 August 16, 1937 and consists briefly, in-drying starch to substantially zero moisture content, Into- 64 Parts of dehydrated starch (of the preferably under vacuum, and then treating the character described in Example 1) thoroughly dehydrated starch, in the absence of atmospheric mix Parts of Pyridin at room temperatureor other water moisture, with a starch inert, The pyridin willreeot w the starch t timze water-immiscible liquid, such as a chlorinated the some t form a ee. whom-starch hydrocarbon, whereby the water immiscible liquid P As st t d in Example 1, t pylene diis adsorbed into the starch to form a relatively chloride may be driven off y hFatingrif desired- 50 stable, anhydrous starch product. The preferred The starch Deste thus Obtained y the p adsorption liquid is propylene dichloride, although cedures above outlined is suitable for general use other chlorinated hydrocarbons and other liquids in the water immiscible field. Since pyridin and such as benzene, solvent naphtha, toluol and the other of the above named reagents, such as like may be employed, formamide, and chloral, are also miscible with both fat and resin solvents, a paste made with any of said reagents in the manner described in this example is readily adaptable for use as an ingredient in paint, lacquer, varnish, plastics and the like. A paste made with a reagent which is not miscible with fat or resin solvents may be employed to advantage in the production of an adhesive.

A specific example of the use of the above paste in the production of a paint is as follows:

Example 3 Percent Anhydrous starch paste (Example 1) 10 White lead Zinc oxide 25 Linseed oil 30 Turpentine 4 Drier, such as litharge 1 These ingredients are thoroughly intermixed and the resulting paint will be found to have superior qualities in several respects. The starch content not only serves as a mere filler, but gives the product a good body, increased adherence, and excellent texture.

In like manner similar results will be obtained by mixing anhydrous starch with other waterimmiscible substances such as lacquers, varnish, plastics, and the like. The principal consideration in each case should be that the liquids mixed with the starch before compounding shall be miscible with the other ingredients of the compound. The ratio between starch and the other substances will, of course, vary with different materials.

For certain purposes the dehydrated starch may be compounded with other water-immiscible substances without first forming an anhydrous starch paste. The following examples illustrate the mixing of dehydrated starch in its dry state with water-immiscible substances.

Example 4 I drous starch, into which has been adsorbed pro- .blend between the various ingredients.

Example 5 Mix together, in a manner specified in Example 1, 150 parts mineral oil, 15 parts of ceresine wax and 5 parts of dehydrated starch, into which has been adsorbed tri-chlor-ethylene in an amount of approximately 10% by weight of the starch.

The resulting product is an excellent lubricant for general purposes.

The above examples are merely illustrative and it is the intention to cover all modifications and variations thereof within the scope of the appended claims.

I claim:

I. A water-free, water-resistant starch paste comprising a mixture of dehydratedstarch having adsorbed therein a water-immiscible liquid which is relatively volatile, organic and neutral in reaction, and an organic starch swelling agent which is miscible with said water immiscible liquid, the swelling agent being of the group consisting of alkyl, aryl and heterocyclic amines and chloral.

2. A water-free, water-resistant starch paste comprising a mixture of substantially 64 parts dehydrated starch having adsorbed therein a Water-immiscible liquid which is relatively volatile, organic and neutral in reaction, and'substantially 100 parts of an organic starch swelling agent which is miscible with said water-immiscible liquid, the swelling agent being of the group consisting of alkyl, aryl and heterocyclic amines and chloral.

3. Method of making a water-free starch paste which comprises mixing dehydrated starch having a water-immiscible liquid adsorbed therein with a water-free organic reagent miscible with said water immiscible liquid and capable of swelling the starch, said reagent being of the group consisting of alkyl, aryl and heterocyclic amines and chloral and said water immiscible liquid being organic relatively volatile and neutral in reaction.

4. Method of making a water-free starch paste which comprises mixing substantially parts of a. dehydrated starch, having a water-immiscible liquid adsorbed therein, with substantially parts of an organic reagent miscible with said Water immiscible liquid and capable of swelling the starch, said reagent being of the group consisting of alkyl, aryl and heterocyclic amines and chlora and said water immiscible liquid being organic relatively volatile and neutral in reaction.

5. Method of making a water-free starch paste which comprises mixing dehydrated starch having a water-immiscible liquid adsorbed therein with an organic reagent which is capable of gelatinizing starch and is miscible with fat and resin solvents, said reagent being of the group consisting of alkyl, aryl and hererocyclic amines and chloral. and said water immiscible liquid being organic relatively volatile and neutral in reaction.

6. Method of making a water-free starch paste which comprises mixing dehydrated starch having a water immiscible liquid adsorbed therein with an amine of the group consisting of alkyl, aryl and heterocyclic amines said water-immiscible liquid being organic, neutral in reaction and relatively volatile.

HAROLD E. BODE. 

